The present invention relates to a synergistically active herbicidal mixture composed of a sulfonylurea derivative (a) of the formula I and one or more herbicidal compounds b1 to 41.
Herbicidally active sulfonylureas of the formula I have been disclosed in the prior art, for example in EP-388 873, EP-559 814, EP-291 851 and DE-40 07 683 and the Conference Proceedings xe2x80x9cFluorine in Agriculturexe2x80x9d, Jan. 9-11 1995, Manchester, chapter xe2x80x9cNew Fluoro Intermediates for Herbicidal Sulfonylureasxe2x80x9d.
Herbicidal compounds b1 to b41 are described, for example, in xe2x80x9cHerbizidexe2x80x9d, Hock, Fedtke, Schmidt, 1st Edition, Thieme 1995 (see xe2x80x9cquincloracxe2x80x9d p. 238, xe2x80x9cmolinatexe2x80x9d p. 32, xe2x80x9cbutachlorxe2x80x9d p. 32, xe2x80x9cpretilachlorxe2x80x9d p. 32, xe2x80x9cdithiopyrxe2x80x9d p. 32, xe2x80x9cmefenacetxe2x80x9d p. 32, xe2x80x9cfenoxapropethylxe2x80x9d p. 216, xe2x80x9cdimepiperatexe2x80x9d p. 32, xe2x80x9cpyrazolatexe2x80x9d p. 146, xe2x80x9cpyrazoxyfenxe2x80x9d p. 146, xe2x80x9cbensulfuron-methylxe2x80x9d p. 31, xe2x80x9cpyrazosulfuron-ethylxe2x80x9d p. 31, xe2x80x9ccinosulfuronxe2x80x9d p. 31, xe2x80x9cbenfuresatexe2x80x9d p. 233, xe2x80x9cbromobutidexe2x80x9d p. 243, xe2x80x9cdymronexe2x80x9d p. 243, xe2x80x9cdimethyametryn xe2x80x9d p. 118, xe2x80x9cesprocarbxe2x80x9d p. 229, xe2x80x9cpyributicarbxe2x80x9d p. 32, xe2x80x9ccinemthylinxe2x80x9d p. 32, xe2x80x9cpropanilxe2x80x9d p. 32, xe2x80x9c2,4-Dxe2x80x9d p. 30, xe2x80x9cbentazonexe2x80x9d p. 30, xe2x80x9cDPX-A-8947xe2x80x9d p. 175, xe2x80x9cmecoprop-Pxe2x80x9d p. 237, xe2x80x9cchlorprophamxe2x80x9d p. 205, xe2x80x9cthiocarbazilxe2x80x9d p. 229, xe2x80x9cethoxyfenxe2x80x9d p. 30, xe2x80x9chaloxyfop-P-methylxe2x80x9d p. 38, xe2x80x9chaloxyfop-ethoxyethylxe2x80x9d p. 38, xe2x80x9cflumiclorac-pentylxe2x80x9d p. 35, xe2x80x9cflupropacilxe2x80x9d p. 143, xe2x80x9cnipyraclofenxe2x80x9d p. 145, xe2x80x9cmetosulamxe2x80x9d p. 33, xe2x80x9cethametsulfuron-methylxe2x80x9d p. 36, xe2x80x9cthifensulfuron-methylxe2x80x9d p. 35 or in xe2x80x9cAgricultural Chemicalsxe2x80x9d, Book II Herbicides, 1993 see xe2x80x9cthiobencarbxe2x80x9d p. 85, xe2x80x9cbenzofenapxe2x80x9d p. 221, xe2x80x9cnapropanilidxe2x80x9d p. 49, xe2x80x9cpiperophosxe2x80x9d p. 102, xe2x80x9canilofosxe2x80x9d p. 241, xe2x80x9cTH-913xe2x80x9d p. 150, xe2x80x9cHW-52xe2x80x9d p. 54, xe2x80x9cICIA-0051xe2x80x9d p. 268, xe2x80x9cpoastxe2x80x9d p. 253, xe2x80x9cfocusxe2x80x9d p. 222, xe2x80x9cdimethenamidxe2x80x9d p. 48, xe2x80x9csulfosaten xe2x80x9d p. 236, xe2x80x9c2,4-DBxe2x80x9d p. 10, xe2x80x9cdichlorprop-Pxe2x80x9d p. 6, xe2x80x9cflupoxamxe2x80x9d p. 44, xe2x80x9cprosulfocarbxe2x80x9d p. 84, xe2x80x9cquinmeracxe2x80x9d p. 233, xe2x80x9cmetazachlorxe2x80x9d p. 64, xe2x80x9cflurtamonexe2x80x9d p. 265, xe2x80x9cbromofenoximxe2x80x9d p. 228, xe2x80x9cfomesafenxe2x80x9d p. 248, xe2x80x9cimazethabenz-methylxe2x80x9d p. 153, xe2x80x9cclodinafopxe2x80x9d p. 214, xe2x80x9cfenoxaprop-P-ethylxe2x80x9d p. 208, xe2x80x9cfluazifop-P-butylxe2x80x9d p. 207, xe2x80x9cquizalofop-P-ethylxe2x80x9d p. 210, xe2x80x9cquizalofop-terfurylxe2x80x9d p. 211, xe2x80x9cflumioxazinxe2x80x9d p. 43, xe2x80x9cflumipropynxe2x80x9d p. 267, xe2x80x9csulfentrazonexe2x80x9d p. 261, xe2x80x9cthiazopyrxe2x80x9d p. 226, xe2x80x9cpyrithiobac-sodiumxe2x80x9d p. 266, xe2x80x9cflumetsulamxe2x80x9d p. 227, xe2x80x9camidosulfuronxe2x80x9d p. 151, xe2x80x9chalosulfuron-methylxe2x80x9d p. 148, xe2x80x9crimsulfuronxe2x80x9d p. 138, xe2x80x9ctribenuron-methylxe2x80x9d p. 139, xe2x80x9ctriflusulfuron-methylxe2x80x9d p. 137, xe2x80x9cprimisulfuronxe2x80x9d p. 147 or in xe2x80x9cShort Review of Herbicides and PGRs 1991, Hodogaya Chemicals see xe2x80x9cfuryloxyfenxe2x80x9d p. 142, xe2x80x9ctriazofenamidxe2x80x9d p. 268, xe2x80x9cKH-218xe2x80x9d p. 52, xe2x80x9cNSK-850xe2x80x9d p. 52, xe2x80x9cJC-940xe2x80x9d p. 90, xe2x80x9cAC-92553xe2x80x9d p. 58, xe2x80x9cbuthidazolexe2x80x9d p. 88, xe2x80x9ccyprazolexe2x80x9d p. 38, xe2x80x9callidochlorxe2x80x9d p. 48, xe2x80x9cbenzoylprop-ethylxe2x80x9d p. 38, xe2x80x9cchlorthiamidxe2x80x9d p. 150 xe2x80x9cdiphenamidxe2x80x9d p. 34, xe2x80x9cflamprop-methylxe2x80x9d p. 40, xe2x80x9cfosaminxe2x80x9d p. 232, xe2x80x9cisoxabenxe2x80x9d p. 42, xe2x80x9cmonalidexe2x80x9d p. 32, xe2x80x9cnaptalamxe2x80x9d p. 36, xe2x80x9cpronamidxe2x80x9d p. 34, xe2x80x9cbialaphosxe2x80x9d p. 234, xe2x80x9cglufosinate-ammoniumxe2x80x9d p. 234, xe2x80x9cglyphosatesxe2x80x9d p. 232, xe2x80x9camitrolxe2x80x9d p. 254, xe2x80x9cclomepropxe2x80x9d p. 20, xe2x80x9cdichlorpropxe2x80x9d p. 6, xe2x80x9cfenopropxe2x80x9d p. 8, xe2x80x9cfluroxypyrxe2x80x9d p. 156, xe2x80x9cMCPAxe2x80x9d p. 4, xe2x80x9cMCPBxe2x80x9d p. 8, xe2x80x9cmecopropxe2x80x9d p. 6, xe2x80x9cnapropamidexe2x80x9d p. 16, xe2x80x9ctriclopyrxe2x80x9d p. 154, xe2x80x9cchlorambenxe2x80x9d p. 28, xe2x80x9cdicambaxe2x80x9d p. 26, xe2x80x9cclomazonexe2x80x9d p. 268, xe2x80x9cdiflufenicanxe2x80x9d p. 42, xe2x80x9cfluorochloridonexe2x80x9d p. 266, xe2x80x9cfluridonexe2x80x9d p. 156, xe2x80x9casulamxe2x80x9d p. 112, xe2x80x9cbarbanxe2x80x9d p. 100, xe2x80x9cbutylatexe2x80x9d p. 106, xe2x80x9ccarbetamidexe2x80x9d p. 36, xe2x80x9cchlorobufamxe2x80x9d p. 100, xe2x80x9ccycloatexe2x80x9d p. 108, xe2x80x9cdesmediphamxe2x80x9d p. 104, xe2x80x9cdi-allatexe2x80x9d p. 106, xe2x80x9cEPTCxe2x80x9d p. 108, xe2x80x9corbencarbxe2x80x9d p. 112, xe2x80x9cpebulatexe2x80x9d p. 106, xe2x80x9cphenisophamxe2x80x9d p. 118, xe2x80x9cpendimediphamxe2x80x9d p. 104, xe2x80x9cprophamxe2x80x9d p. 100, xe2x80x9csulf-allatexe2x80x9d p. 110, xe2x80x9cterbucarbxe2x80x9d p. 102, xe2x80x9ctri-allatexe2x80x9d p. 108, xe2x80x9cvernolatexe2x80x9d p. 108, xe2x80x9cacetochlorxe2x80x9d p. 48, xe2x80x9calachlorxe2x80x9d p. 46, xe2x80x9cdiethathyl-ethylxe2x80x9d p. 48, xe2x80x9cdimethachlorxe2x80x9d p. 50, xe2x80x9cmetolachlorxe2x80x9d p. 46, xe2x80x9cpropachlorxe2x80x9d p. 44, xe2x80x9cpyrnachlorxe2x80x9d p. 44, xe2x80x9cterbuchlorxe2x80x9d p. 48, xe2x80x9cxylachlorxe2x80x9d p. 52, xe2x80x9calloxydimxe2x80x9d p. 260, xe2x80x9cclethodimxe2x80x9d p. 270, xe2x80x9ccloproxydimxe2x80x9d p. 268, xe2x80x9ctralkoxydimxe2x80x9d p. 270, xe2x80x9cdalaponxe2x80x9d p. 212, xe2x80x9cethofumesatexe2x80x9d p. 124, xe2x80x9cbenefinxe2x80x9d p. 54, xe2x80x9cbutralinxe2x80x9d p. 58, xe2x80x9cdinitraminxe2x80x9d p. 56, xe2x80x9cethalfluralinxe2x80x9d p. 60, xe2x80x9cfluchloralinxe2x80x9d p. 54, xe2x80x9cisopropalinxe2x80x9d p. 58, xe2x80x9cnitralinxe2x80x9d p. 58, xe2x80x9coryzalinxe2x80x9d p. 60, xe2x80x9cprodiaminexe2x80x9d p. 62, xe2x80x9cprofluralinxe2x80x9d p. 54, xe2x80x9ctrifluralinxe2x80x9d p. 54, xe2x80x9cdinosebxe2x80x9d p. 128, xe2x80x9cdinoseb-acetatexe2x80x9d p. 128, xe2x80x9cdinoterbxe2x80x9d p. 128, xe2x80x9cDNOCxe2x80x9d p. 126, xe2x80x9cacilfluorfen-sodiumxe2x80x9d p. 142, xe2x80x9caclonifenxe2x80x9d p. 146, xe2x80x9cbifenoxxe2x80x9d p. 140, xe2x80x9cchlornitrofenxe2x80x9d p. 138, xe2x80x9cdifenoxuronxe2x80x9d p. 76, xe2x80x9cfluorodifenxe2x80x9d p. 138, xe2x80x9cfluoroglycofen-ethylxe2x80x9d p. 146, xe2x80x9clactofenxe2x80x9d p. 144, xe2x80x9cnitrofenxe2x80x9d p. 136, xe2x80x9cnitrofluorfenxe2x80x9d p. 140, xe2x80x9coxyfluorfenxe2x80x9d p. 140, xe2x80x9ccyperquatxe2x80x9d p. 158, xe2x80x9cdifenzoquatxe2x80x9d p. 160, xe2x80x9cdiquatxe2x80x9d p. 158, xe2x80x9cparaquatxe2x80x9d p. 158, xe2x80x9cbenzthiazuronxe2x80x9d p. 82, xe2x80x9cbuturonxe2x80x9d p. 66, xe2x80x9cchlorbromuronxe2x80x9d p. 72, xe2x80x9cchloroxuronxe2x80x9d p. 76, xe2x80x9cchlortoluronxe2x80x9d p. 74, xe2x80x9ccycluronxe2x80x9d p. 84, xe2x80x9cdimeturonxe2x80x9d p. 88, xe2x80x9cdiuronxe2x80x9d p. 70, xe2x80x9cethidimuronxe2x80x9d p. 86, xe2x80x9cfenuronxe2x80x9d p. 64, xe2x80x9cfluometuronxe2x80x9d p. 68, xe2x80x9cisoproturonxe2x80x9d p. 80, xe2x80x9cisouronxe2x80x9d p. 88, xe2x80x9ckarbutilatexe2x80x9d p. 76, xe2x80x9clinuronxe2x80x9d p. 72, xe2x80x9cmethabenzthiazuronxe2x80x9d p. 82, xe2x80x9cmetoxuronxe2x80x9d p. 72, xe2x80x9cmonolinuronxe2x80x9d p. 66, xe2x80x9cmonuronxe2x80x9d p. 64, xe2x80x9cneburonxe2x80x9d p. 72, xe2x80x9csiduron xe2x80x9d p. 68, xe2x80x9ctebuthiuronxe2x80x9d p. 86, xe2x80x9ctrimeturonxe2x80x9d p. 64, xe2x80x9cisocarbamidxe2x80x9d p. 168, xe2x80x9cimazamethapyrxe2x80x9d p. 172, xe2x80x9cimazapyrxe2x80x9d p. 170, xe2x80x9cimazaquinxe2x80x9d p. 170, xe2x80x9cimazethapyrxe2x80x9d p. 172, xe2x80x9cmethazolexe2x80x9d p. 162, xe2x80x9coxadiazonxe2x80x9d p. 162, xe2x80x9ctridiphanexe2x80x9d p. 266, xe2x80x9cbromoxynilxe2x80x9d p. 148, xe2x80x9cioxynilxe2x80x9d p. 148, xe2x80x9cdiclofop-methylxe2x80x9d p. 16, xe2x80x9cfenthiaprop-ethylxe2x80x9d p. 20, xe2x80x9cfluazifop-butylxe2x80x9d p. 18, xe2x80x9chaloxyfop-methylxe2x80x9d p. 18, xe2x80x9cisoxapyrifopxe2x80x9d p. 22, xe2x80x9cpropaquizafopxe2x80x9d p. 24, xe2x80x9cquizalofop-ethylxe2x80x9d p. 20, xe2x80x9cchlorfenacxe2x80x9d p. 258, xe2x80x9cchlorophenprop-methylxe2x80x9d p. 258, xe2x80x9cchloridazonxe2x80x9d p. 174, xe2x80x9cmaleic hydrazidexe2x80x9d p. 162, xe2x80x9cnorflurazonxe2x80x9d p. 174, xe2x80x9cpyridatexe2x80x9d p. 176, xe2x80x9cclopyralidxe2x80x9d p. 154, xe2x80x9cpicloram,xe2x80x9d p. 154, xe2x80x9cchlorimuron-ethylxe2x80x9d p. 92, xe2x80x9cchlorsulfuronxe2x80x9d p. 92, xe2x80x9cflazasulfuronxe2x80x9d p. 96, xe2x80x9cmetsulfuron-methylxe2x80x9d p.92, xe2x80x9cnicosulfuronxe2x80x9d p. 96, xe2x80x9csulfometuron-methylxe2x80x9d p. 92, xe2x80x9ctriasulfuronxe2x80x9d p. 94, xe2x80x9cametrynxe2x80x9d p. 198, xe2x80x9catrazinexe2x80x9d p. 188, xe2x80x9caziprotrynexe2x80x9d p. 206, xe2x80x9ccyanazinexe2x80x9d p. 192, xe2x80x9ccyprazinexe2x80x9d p. 192, xe2x80x9cdesmetrynexe2x80x9d p. 200, xe2x80x9cdipropetrynxe2x80x9d p. 202, xe2x80x9ceglinazine-ethylxe2x80x9d p. 208, xe2x80x9chexazinonxe2x80x9d p. 208, xe2x80x9cprocyazinexe2x80x9d p. 192, xe2x80x9cprometonexe2x80x9d p. 196, xe2x80x9cprometrynxe2x80x9d p. 196, xe2x80x9cpropazinexe2x80x9d p. 188 xe2x80x9csecbumetonxe2x80x9d p. 196, xe2x80x9csimazinexe2x80x9d p. 188, xe2x80x9csimetrynxe2x80x9d p. 196, xe2x80x9cterbumetonxe2x80x9d p. 204, xe2x80x9cterbutrynxe2x80x9d p. 198, xe2x80x9cterbuthylazinexe2x80x9d p. 190, xe2x80x9ctrietazinexe2x80x9d p. 188, xe2x80x9cethiozinxe2x80x9d p. 210, xe2x80x9cmetamitronxe2x80x9d p. 206, xe2x80x9cmetribuzinxe2x80x9d p. 202, xe2x80x9cbromacilxe2x80x9d p. 180, xe2x80x9clenacilxe2x80x9d p. 180, xe2x80x9cterbacilxe2x80x9d p. 180, xe2x80x9cbenazolinxe2x80x9d p. 262, xe2x80x9cbensulidexe2x80x9d p. 228, xe2x80x9cbenzofluorxe2x80x9d p. 266, xe2x80x9cbutamifosxe2x80x9d p. 228, xe2x80x9cDCPAxe2x80x9d p. 28, xe2x80x9cdichlobenilxe2x80x9d p. 148, xe2x80x9cendothalxe2x80x9d p. 264, xe2x80x9cmefluididexe2x80x9d p. 306, xe2x80x9cperfluidonexe2x80x9d p. 260, xe2x80x9cterbuchlorxe2x80x9d p. 48 or in xe2x80x9cGlobal Herbicide Directoryxe2x80x9d First Edition, 1994 see xe2x80x9coxadiargylxe2x80x9d p. 96, or in xe2x80x9cEuropean Directory of Agrochemical Products Volume 2xe2x80x94Herbicidesxe2x80x9d Fourth Edition, see xe2x80x9cbuminafosxe2x80x9d p. 255. The compound xe2x80x9cDEH-112xe2x80x9d is disclosed in European Patent Application EP 0 302 203. The compound xe2x80x9ccaloxydimxe2x80x9d is described in DE 3 336 140, the compound xe2x80x9ccinidon-ethylxe2x80x9d in DE 3 603 789 and the compound xe2x80x9cfluorbentranilxe2x80x9d in EP 84 893. xe2x80x9cOther compounds are known from xe2x80x9cBrighton Crop Protection Conferencexe2x80x94Weeds xe2x80x941993 (see xe2x80x9cthidiaziminxe2x80x9d p. 29, xe2x80x9cAC-322140xe2x80x9d p. 41, xe2x80x9cKIH-6127xe2x80x9d p. 47, xe2x80x9cprosulfuronxe2x80x9d p. 53, xe2x80x9cKIH-2023xe2x80x9d p. 61, xe2x80x9cmetobenzuronxe2x80x9d p. 67). The compound xe2x80x9cCH-900xe2x80x9d is described in EP 0 332 133.
In principle, it is desirable in crop protection products to increase the specific activity of an active ingredient and the reliability of its action. It was therefore the object of the present invention to increase the activity of known, herbicidally active sulfonylureas of the formula I.
We have found that this object is achieved by a herbicidal mixture which comprises.
a) at least one derivative of the sulfonylurea of the formula I: 
xe2x80x83where the substituents have the following meanings:
R1 is C1-C6-alkyl which has attached to it one to five of the following groups: methoxy, ethoxy, SO2CH3, cyano, chlorine, fluorine, SCH3, S(O)CH3; halogen; a group ER6 where E is O, S or NR7; COOR8; NO2; S(O)oR9, SO2NR10R11, CONR10R11;
R2 is hydrogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, halogen, C1-C4-alkoxy, C1-C4-haloalkoxy; C1-C4-haloalkyl, a C1-C2--alkylsulfonyl group, nitro, cyano or C1-C4-alkylthio;
R3 is F, CF3, CF2Cl, CF2H, OCF3, OCF2Cl, or, if R1 is CO2CH3 and R2 is simultaneosly fluorine, R3 is Cl, or, if R1 is CH2CF3 or CF2CF3, R3 is methyl, or, if R4 is OCF3 or OCF2Cl, R3 is OCF2H or OCF2Br;
R4 is C1-C2-alkoxy, C1-C2-alkyl, C1-C2-alkylthio, C1-C2-alkylamino, di-C1-C2-alkylamino, halogen, C1-C2-haloalkyl, C1-C2-haloalkoxy,
R5 is hydrogen, C1-C2-alkoxy, C1-C4-alkyl;
R6 is C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl or C3-C6-cycloalkyl, all of which can have attached to them. 1 to 5 halogen atoms, with the exception of allyl, difluoromethoxy, chlorodifluoromethoxy and 2-chloroethoxy, if E is O or S. In the event that E is O or NR7, R6 is furthermore also methylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl, allylsulfonyl, propargylsulfonyl or dimethylsulfamoyl;
R7 is hydrogen, methyl or ethyl
R8 is a C1-C6-alkyl group which can have attached to it up to three of the following radicals: halogen, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkoxy, C1-C4-alkoxy-C1-C2-alkoxy, C3-C7-cycloalkyl and/or phenyl; a C5-C7-cycloalkyl group which can have attached to it up to three C1-C4-alkyl groups; C3-C6-alkenyl or C3-C6-alkynyl;
R9 is a C1-C6-alkyl group which can have attached to it one to three of the following radicals: halogen, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkoxy, C1-C4-alkoxy-C1-C2-alkoxy, C3-C7-cycloalkyl and/or phenyl; a C5-C7-cycloalkyl group which can have attached to it one to three C1-C4-alkyl groups; a C3-C6-alkenyl group or a C3-C6-alkynyl group;
R10 is hydrogen, a C1-C2-alkoxy group, a C1-C6-alkyl group, or together with R11 is a C4-C6-alkylene chain in which one methylene group can be replaced by an oxygen atom or a C1-C4-alkylimino group;
R11 is a C1-C4-alkyl group which can have attached to it one to four halogen or C1-C4-alkoxy radicals; C3-C6-cycloalkyl
n is 0-3
o is 1-2
Z N or CH, and
b) a synergistically active amount of at least one herbicidal compound selected from the groups b1 to b41
b1 1,3,4-thiadiazoles: buthidazole, cyprazole
b2 amides: allidochlor (CDAA), benzoylprop-ethyl, bromobutide, chlorthiamid, dimepiperate, dimethenamid, diphenamid, etobenzanid (benzchlomet), flamprop-methyl, fosamin, isoxaben, monalide, naptalame, pronamid (propyzamid), propanil
b3 aminophosphoric acids: bilanafos, (bialaphos), buminafos, glufosinate-ammonium, glyphosate, sulfosate
b4 aminotriazoles: amitrol
b5 anilides: anilofos, mefenacet
b6 aryloxyalkanoic acids: 2,4-D, 2,4-DB, clomeprop, dichlorprop, dichlorprop-P, dichlorprop-P (2,4-DP-P), fenoprop (2,4,5-TP), fluoroxy-pyr, MCPA, MCPB, mecoprop, mecoprop-P, napropamide, napropanilide, triclopyr
b7 benzoic acids: chloramben, dicamba
b8 benzothiadiazinones: bentazone
b9 bleaches: clomazone (dimethazone), diflufenican, fluorochloridone, flupoxam, fluridone, pyrazolate, sulcotrione (chlormesulone)
b10 carbamates: asulam, barban, butylate, carbetamid, chlorbufam, chlorpropham, cycloate, desmedipham, di-allate, EPTC, esprocarb, molinate, orbencarb, pebulate, phenisopham, phenmedipham, propham, prosulfocarb, pyributicarb, sulf-allate (CDEC), terbucarb, thiobencarb (benthiocarb), tiocarbazil, tri-allate, vernolate
b11 quinolinecarboxylic acids: quinclorac, quinmerac
b12 chloracetanilides: acetochlor, alachlor, butachlor, butenachlor, diethatylethyl, dimethachlor, metazachlor, metolachlor, pretilachlor, propachlor, prynachlor, terbuchlor, thenylchlor, xylachlor
b13 cyclohexenones: alloxydim, caloxydim, clethodim, cloproxydim, cycloxydim, sethoxydim, tralkoxydim, 2-{1-[2-(4-chlorophenoxy)propyloxyimino]butyl}-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohexen-1-one
b14 dichloropropionic acids: dalapon
b15 dihydrobenzofurans: ethofumesate
b16 dihydrofuran-3-ones: flurtamone
b17 dinitroanilines: benefin, butralin, dinitramin, ethalfluralin, fluchloralin, isopropalin, nitralin, oryzalin, pendimethalin, prodiamine, profluralin, trifluralin
b18 dinitrophenols: bromofenoxim, dinoseb, dinoseb-acetate, dinoterb, DNOC
b19 diphenyl ethers: acifluorfen-sodium, aclonifen, bifenox, chlornitrofen (CNP), difenoxuron, ethoxyfen, fluorodifen, fluoroglycofen-ethyl, fomesafen, furyloxyfen, lactofen, nitrofen, nitrofluorfen, oxyfluorfen
b20 dipyridylenes: cyperquat, difenzoquat methylsulfate, diquat, paraquat dichloride
b21 ureas: benzthiazuron, buturon, chlorbromuron, chloroxuron, chlortoluron, cumyluron, dibenzyluron, cycluron, dimefuron, diuron, dymrone, ethidimuron, fenuron, fluometuron, isoproturon, isouron, karbutilate, linuron, methabenzthiazuron, metobenzuron, metoxuron, monolinuron, monuron, neburon, siduron, tebuthiuron, trimeturon
b22 imidazoles: isocarbamid
b23 imidazolinones: imazamethapyr, imazapyr, imazaquin, imazethabenz-methyl (imazame), imazethapyr
b24 oxadiazoles: methazole, oxadiargyl, oxadiazon
b25 oxiranes: tridiphane
b26 phenols: bromoxynil, ioxynil
b27 phenoxyphenoxypropionic esters: clodinafop, cyhalofop-butyl, diclofop-methyl, fenoxapropethyl, fenoxaprop-P-ethyl, fenthiapropethyl, fluazifopbutyl, fluazifop-P-butyl, haloxyfop-ethoxyethyl, haloxy-fop-methyl, haloxyfop-P-methyl, isoxapyrifop, propaquizafop, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-tefuryl
b28 phenylacetic acids: chlorfenac (fenac)
b29 phenylpropionic acid: chlorophenprop-methyl
b30 protoporphyrinogen IX oxydase inhibitors: benzofenap, cinidon-ethyl, flumiclorac-pentyl, flumioxazin, flumipropyn, flupropacil, fluthiacet-methyl, pyrazoxyfen, sulfentrazone, thidiazimin
b31 pyrazoles: nipyraclofen
b32 pyridazines: chloridazon, maleic hydrazide, norflurazon, pyridate
b33 pyridinecarboxylic acids: clopyralid, dithiopyr, picloram, thiazopyr
b34 pyrimidyl ethers: pyrithiobac acid, pyrithiobac sodium, KIH-2023, KIH-6127
b35 sulfonamides: flumetsulam, metosulam
b36 sulfonylureas: amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, halosulfuron-methyl, imazosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-methyl, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, triflusulfuron-methyl
b37 triazines: ametryn, atrazine, aziprotryn, cyanazine, cyprazine, desmetryn, dimethamethryn, dipropetryn, eglinazine-ethyl, hexazinon, procyazine, prometon, prometryn, propazine, secbumeton, simazine, simetryn, terbumeton, terbutryn, terbuthylazine, trietazine
b38 triazinones: ethiozin, metamitron, metribuzin
b39 triazolecarboxamides: triazofenamid
b40 uracils: bromacil, lenacil, terbacil
b41 others: benazolin, benfuresate, bensulide, benzofluor, butamifos, cafenstrole, chlorthal-dimethyl (DCPA), cinmethylin, dichlobenil, endothall, fluorbentranil, mefluidide, perfluidone, piperophos
or their environmentally compatible salts.
The herbicidal mixture according to the invention has superadditive synergistic action and is selective for those crop plants which also tolerate the individual compounds themselves.
Especially preferred sulfonylureas of the formula I with a view to their synergistic herbicidal action are those where
R1 is CO2CH3, CO2C2H5, CO2iC3H7, CF3, CF2H; OSO2CH3, OSO2N(CH3)2, Cl, NO2, SO2N(CH3)2, SO2CH3 and N(CH3)SO2CH3 
R2 is hydrogen, Cl, F or C1-C2-alkyl
R3 is CF2H, OCF3, OCF2Cl, CF2Cl, CF3 or F
R4 is OCH3, OC2H5, OCF3, OCF2Cl; CF3, Cl, F, NH(CH3), N(CH3)2 or C1-C2-alkyl
R5 hydrogen,
Z N or CH and
n 0 or 1.
preferred compounds of the formula I are compiled in the table which follows.
Examples of preferred compounds (b) are:
bromobutide
dimethenamid
isoxaben
propanil
glufosinate-ammonium
glyphosate
sulfosate
mefenacet
2,4-D
2,4-DB
2,4-DBEE
dichlorprop
dichlorprop-P
dichlorprop-P (2,4-DP-P)
fluroxypyr
MCPA
mecoprop
mecoprop-P
dicama
bentazone
clomazone
diflufenican
sulcotrione
phenmedipham
thiobencarb
quinclorac
quinmerac
acetochlor
alachlor
butachlor
metazachlor
metolachlor
pretilachlor
butroxydim
caloxydim
clethodim
cycloxydim
sethoxydim
tralkoxydim
2-{1[-2-(4-chlorophenoxy)propyloxyimino]butyl}-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohexen-1-one
pendimethalin
acifluorfen-sodium
bifenox
fluoroglycofen-ethyl
fomesafen
lactofen
chlortoluron
cycluron
dymrone
isoproturon
methabenzthiazuron
imazaquin
imazethabenz-methyl
imazethapyr
bromoxynil
ioxynil
clodinafop
cyhalofop-butyl
fenoxyprop-ethyl
fenoxaprop-P-ethyl
haloxyfop-P-methyl
cinidon-ethyl
flumiclorac-pentyl
flumipropyn
fluthiacet-methyl
pyridate
clopyralid
bispyribac-sodium
KIH-8555
KUH-920
flumetsulam
metosulam
amidosulfuron
azimsulfuron
bensulfuron-methyl
chlorimuron-ethyl
chlorsulfuron
cinosulfuron
cyclosulfamuron
ethoxysulfuron
flazasulfuron
halosulfuron-methyl
HOE-107925
imazosulfuron
metsulfuron-methyl
nicosulfuron
primisulfuron
prosulfuron
pyrazosulfuron-ethyl
rimsulfuron
thifensulfuron-methyl
triasulfuron
tribenuron-methyl
atrazine
cyanazine
terbuthylazine
benazolin
benfuresate
cafenstrole
cinemthylin
ammonium-bentazone
cloquintocet
ET-751
F-8426
KPP-314
The following compounds are particularly preferred:
2,4-D
dichlorprop-P
MCPA
mecoprop-P
dicamba
bentazone
diflufenican
sulcotrione
quinclorac
caloxydim
cycloxydim
sethoxydim
2-{1-[2-(4-chlorophenoxy)propyloxyimino]butyl}-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohexen-1-one
acifluorfen-sodium
fluoroglycofen-ethyl
bromoxynil
fenoxyprop-ethyl
cinidon-ethyl
amidosulfuron
bensulfuron-methyl
metsulfuron-methyl
nicosulfuron
pyrazosulfuron-ethyl
rimsulfuron
triasulfuron
tribenuron-methyl
atrazine
terbuthylazine
ammonium-bentazone
cloquintocet
The following compounds are very especially preferred:
dichlorprop-P
mecoprop-P
ammonium-bentazone
bentazone
diflufenican
quinclorac
2-(1-[2-(4-chlorophenoxy)propyloxyimino]butyl)-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohexen-1-one
caloxydim
cycloxydim
sethoxydim
fluoroglycofen-ethyl
cinidon-ethyl
nicosulfuron
pyrazosulfuron-ethyl
rimsulfuron
atrazine
terbuthylazine.
The present invention also relates to herbicidal compositions which comprise at least one herbicidally active amount of a sulfonylurea (a) of the above-described formula I or their environmentally compatible salts, a synergistically active amount of at least one above-described herbicidal compound (b) or its environmentally compatible salts, at least one liquid and/or solid carrier and, if desired, at least one adjuvant.
In the herbicidal mixtures and herbicidal compositions according to the invention, the sulfonylureas of the formula I or their environmentally compatible salts and the herbicidal compounds (b) or their environmentally compatible salts are used in such weight ratios that the desired synergistic effect is observed. The mixing ratios of sulfonylurea of the formula I and a herbicidal compound (b) are preferably 1: to 1:0.1 to 1:40, in particular 1:0.2 to 1:20, especially preferably 1:0.5 to 1:15.
The herbicidal mixtures and herbicidal compositions according to the invention which comprise the sulfonylureas of the formula I or their environmentally compatible salts of, for example, alkali metals, alkaline earth metals or ammonia and amines and the herbicidal compounds (b) or their environmentally compatible salts of, for example, alkali metals, alkaline earth metals or ammonia and amines are capable of effecting very good control of broad-leaved weeds and grass weeds in the crop rice without damaging the crop plants, an effect which is observed even when low rates of application are used.
Taking into consideration the versatility of the application methods, the herbicidal mixtures and herbicidal compositions according to the invention can also be employed in a further number of crop plants for eliminating undesirable plants. Suitable crops are, for example, the following:
Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris ssp. altissima, Beta vulgaris ssp. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spp., Manihot esculenta, Medicago sativa, Musa spp., Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spp., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera, Zea mays, 
In addition, the herbicidal mixtures and herbicidal compositions according to the invention can also be used in crops which tolerate the action of herbicides due to breeding, including genetic engineering methods.
The herbicidal mixtures and herbicidal compositions according to the invention may be applied pre- or post-emergence. If the active ingredients are less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are sprayed, with the aid of the spraying equipment, in such a way that the active ingredients reach the leaves of the sensitive crop plants as little as possible while reaching the leaves of undesirable plants which grow underneath, or the bare soil surface (post-directed, lay-by).
The compositions according to the invention can be applied, for example in the form of ready-to-spray aqueous solutions, powders, suspensions, also highly-concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend on the intended purposes; in any case, they should guarantee the finest possible distribution of the active ingredients according to the invention.
Suitable inert additives are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg. paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone or strongly polar solvents such as N-methylpyrrolidone or water.
Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetting agent, adhesive, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active ingredient, wetting agent, adhesive, dispersant or emulsifier and, if desired, solvent or oil, which are suitable for dilution with water.
Suitable surfactants are the alkali, alkaline earth and ammonium salts of aromatic sulfonic acids, eg. ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol or nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignosulfite waste liquors or methylcellulose.
Powders, materials for spreading, and dusts, can be prepared by mixing or concomitantly grinding the herbicidal mixture with a solid carrier.
Granules, eg. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredient onto solid carriers. Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders, or other solid carriers.
In general, the formulations comprise 0.01 to 95% by weight, preferably 0.5 to 90% by weight, of the herbicidal mixture.
It may furthermore be advantageous to apply the herbicidal mixtures and herbicidal compositions according to the invention together in the form of a mixture with other crop protection agents, for example with agents for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are employed for treating nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added.
The rates of application of pure herbicidal mixture, ie. without formulation auxiliaries, are from 0.01 to 5 kg/ha, preferably 0.03 to 4 kg/ha, especially preferably 0.1 to 3.0 kg/ha, of active ingredient (a.i.), depending on the intended purpose, the season, the target plants and the growth stage.
The herbicidal compositions according to the invention are applied to the plants mainly by means of foliar sprays. They may be applied by customary spraying techniques using amounts of approximately 100 to 1000 1 of spray mixture per ha, for example using water as the carrier. An application of the compositions in the so-called xe2x80x9clow-volumexe2x80x9d and xe2x80x9cultra-low-volumexe2x80x9d method is also possible, as is their application in the form of so-called granules.